EP0306334B1 - Ligands macrocycliques liés à de la silice ou du gel de silice et leur utilisation pour enlever et concentrer sélectivement et quantitativement des ions présents à faible concentration de mélanges contenant d'autres ions - Google Patents

Ligands macrocycliques liés à de la silice ou du gel de silice et leur utilisation pour enlever et concentrer sélectivement et quantitativement des ions présents à faible concentration de mélanges contenant d'autres ions Download PDF

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EP0306334B1
EP0306334B1 EP88308158A EP88308158A EP0306334B1 EP 0306334 B1 EP0306334 B1 EP 0306334B1 EP 88308158 A EP88308158 A EP 88308158A EP 88308158 A EP88308158 A EP 88308158A EP 0306334 B1 EP0306334 B1 EP 0306334B1
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group
silica
silica gel
atom
oxygen atom
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EP0306334A3 (en
EP0306334A2 (fr
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Jerald S. Bradshaw
Izaat Reed M.
Ronald L. Bruening
James J. Christensen
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Brigham Young University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
    • B01J20/3263—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. an heterocyclic or heteroaromatic structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/005—Preparation involving liquid-liquid extraction, absorption or ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention comprises a composition of matter and a process of using it.
  • the composition of matter comprises silica, e.g. sand or silica gel, having a covalent bond to certain macrocyclic compounds through a hydrocarbon chain with or without an ether oxygen linkage.
  • a composition of matter comprises silica covalently bonded to a macrocyclic compound and having the formula I, II, III, IV or V below: in which A to F each separately represent an oxygen atom or a sulphur atom or an N-R group in which R represents a hydrogen atom or an alkyl group preferably lower alkyl, e.g. C1-C4 alkyl, or an aryl group, preferably phenyl alkyl or lower alkyl, e.g.
  • phenyl, or benzyl n is 0, 1, 2, 3 or 4
  • Z represents silica or silica gel
  • X represents an alkyl group, preferably methyl or ethyl, or an aryl group e.g. phenyl, or an alkoxy group e.g. methoxy or ethoxy or a halogen atom e.g.
  • a to F each separately represent an oxygen atom or a sulphur atom or an N-R group in which R represents a hydrogen atom or an alkyl group, preferably lower alkyl, e.g. C1-C4 alkyl, or an aryl group, preferably phenyl alkyl or lower alkyl, e.g.
  • Z represents silica or silica gel
  • X represents an alkyl group, preferably methyl or ethyl, or an aryl group e.g. phenyl, or alkoxy group e.g. methoxy or ethoxy or a halogen atom e.g. a chlorine atom or an O-silica group or an O-silica gel group
  • Y represents an oxygen atom or a CH2 group; or in which n is 0, 1 or 2
  • Z represents silica or silica gel
  • X represents an alkyl group preferably methyl or ethyl, or an aryl group, e.g.
  • phenyl or an alkoxyl group e.g. methoxy or ethoxy, or a halogen atom or an O-silica group or an O-silica gel group
  • Y represents an oxygen atom or a CH2 group; or in which n is 0, 1 or 2
  • Z represents silica or silica gel
  • R represents an alkyl group or an aryl group and X represents an alkyl group or an aryl group or an alkoxyl group or a halogen atom or an O-silica group or an O-silica gel group
  • Y represents an oxygen atom or a CH2 group; or in which l is 0, 1 or 2
  • Z represents silica or silica gel
  • R represents a hydrogen atom or an alkyl group preferably lower alkyl, e.g.
  • C1 -C4 alkyl or an aryl group, preferably phenyl alkyl or lower alkyl, e.g. C1-C4, phenyl, or benzyl
  • X represents an alkyl group, preferably methyl or ethyl, or an aryl group e.g. phenyl, or alkoxy group e.g. methoxy or ethoxy or a halogen atom e.g. a chlorine atom or an O-silica group or an O-silica gel group
  • Y represents an oxygen atom or a CH2 group.
  • R may represent a hydrogen atom or an alkyl group or a benzyl group and X may represent an alkyl group or a chlorine atom or an O-silica group, and Y represents an oxygen atom.
  • Y represents an oxygen atom and X may represent a methyl group, a chlorine atom or an O-silica group.
  • Y represents an oxygen atom
  • R represents a methyl group, a chlorine atom or an O-silica group.
  • V Y represents an oxygen atom
  • R represents a hydrogen atom or an alkyl group or a benzyl group
  • X represents a methyl group or an O-silica group.
  • the silica may be sand.
  • a to F each represent an oxygen atom, n is 0, 1 or 2 and X represents a methyl group or a chlorine atom or an O-silica group or an O-silica gel group; and in Formula II, A to F each represent an oxygen atom, , m and n each are 1, and X represents a methyl group or a chlorine atom or an O-silica group or an O-silica gel group.
  • A, C, D and F each represent an oxygen atom and B and E each represent any N-R group in which R represents a hydrogen atom or any alkyl group or any benzyl group, n is 0, 1 or 2, and X represents a methyl group or a chlorine atom or an O-silica group or an O-silica gel group.
  • a to F each represent an oxygen atom
  • m and n each are 1 and is 0, 1 or 2
  • X represents a methyl group or a chlorine atom or an O-silica gel group
  • Z represents an O-silica gel group.
  • the process comprises selectively and quantitatively removing and concentrating a selected ion or group of ions present at low concentrations from a plurality of other ions in a multiple ion solution in which the other ions may be present at much higher concentrations by bringing the multiple ion solution into contact with a composition of matter in accordance with the present invention.
  • the preferred embodiment disclosed herein involves carrying out the process by bringing a large volume of the multiple ion solution into contact with a compound of the invention as an addition compound to silica preferably in the form of sand or silica gel in a separation column through which the mixture is first flowed to complex the desired ion or ions with the said compound followed by the flow through the column of a small volume of a receiving liquid to break the complex by chemical or thermal means, dissolve the desired ions and carry them out of the column.
  • Other equivalent apparatus may be used instead of a column, e.g. a slurry which is filtered, washed with a receiving liquid to break the complex and recover the desired ion.
  • the desired metal ions are then recovered from the receiving phase by well known procedures.
  • the process comprises forming a chemical covalent bond between silica, preferably as sand or silica gel, and at least one of the compounds, placing the resulting bonded silica compound in a contacting device such as a tall column, causing a large volume of the mixture of ions to flow through the column where the desired ions complex with the bonded silica compound which separates them from the rest of the mixture which flows out of the column, then flowing a small volume of the receiving liquid through the column to break the complex and dissolve and carry out of the column the desired ion(s).
  • the desired metal ions are then recovered from the receiving liquid by well known procedures.
  • macrocyclic polyethers and other macrocyclic ligands present as solutes in a solvent such as water are characterised by their ability to selectively form strong bonds with particular ions or groups of ions present as solutes in the same solvent according to size, donor atom-related and other well known selectivity rules as noted in articles by R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D. Lamb, J.J. Christensen, and D. Sen, THERMODYANMIC AND KINETIC DATA FOR CATION-MACROCYCLE INTERACTION , Chem. Rev., 1985, 271-339 and by L.F.
  • the compounds of the present invention comprise certain macrocyclic ligands covalently bonded to silica, e.g. sand or silica gel.
  • the compounds are identified above.
  • the process of the present invention uses the compounds, which are characterised by high selectivity for and removal of desired metal ions or groups of metal ions present at low concentrations from the source phase containing a mixture of metal ions with the ions one does not desire to remove frequently present in much greater concentrations in the solution, in a separation device such as a column through which the solution is flowed.
  • the process of selectively removing and concentrating the desired ion(s) is characterised by the ability to quantitatively complex from a large volume of solution the desired ion(s) when they are present at low concentrations.
  • the said ions are recovered from the separation column by flowing through it a small volume of a receiving phase which contains a solubilizing reagent which need not be selective, but which will strip the ions from the macrocyclic ligand quantitatively.
  • a solubilizing reagent which need not be selective, but which will strip the ions from the macrocyclic ligand quantitatively.
  • Macrocycles which do not contain electron withdrawing groups and which are capable of being bonded to silica must be synthesized. Then the macrocycle must be covalently bonded to the sand or silica gel.
  • One method of preparing the compounds of Formula I for example is to react the allyloxy forms of the crowns with chlorodimethylsilane (or dichloromethylsilane) followed by heating the resulting chlorosilane (or dichlorosilane) with silica as follows:
  • a method of preparing the macrocyclic compounds of Formula III is to react 4-allyloxypyridino-18-crown-6 with chlorodimethylsilane (or dichloromethylsilane) and heating the resulting chlorosilane and silica as follows:
  • this bonded macrocycle will not differ from those of the unsubstituted macrocycle present as a solute in solution when such a macrocycle does not contain electron withdrawing substituent groups and the bonding to sand or silica gel does not occur via one of the macrocycle donor atoms. This will now be described in more detail in the following description of the metal ion recovery and concentration process.
  • the metal ion recovery and concentration process of the invention relates to the selective recovery of desired metal ions from mixtures thereof with other metal ions using the compounds of the invention as defined above.
  • Effective methods of recovery and/or separation of metal ions, particularly silver, lead, cadmium, and other heavy metals, from one another in culinary water supplies, waste solutions, deposits and industrial solutions and silver recovery from waste solutions, e.g. from emulsions on photographic and X-ray film, represent a real need in modern technology. These ions are typically present at low concentrations in solutions containing other ions at much greater concentrations. Hence, there is a real need for a process to selectively recover and concentrate these hazardous and/or desirable ions.
  • the present invention accomplishes this separation effectively and efficiently by the use of compounds selected from the families represented by the formulae I to V.
  • the process first involves selecting a macrocycle-bonded silica where the particular macrocycle will selectively complex the ion(s) of interest.
  • a large data base for measurements of macrocycle-ion interactions where the macrocycle is unsubstituted and present as a solute in a solvent.
  • Much of this data base is presented in an article by R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D. Lamb, J.J. Christensen, and D. Sen, THERMODYNAMIC AND KINETIC DATA FOR CATION-MACROCYCLE INTERACTION , Chem. Rev. Vol. 23, 271-339 (1985).
  • this data base has only provided general qualitative predictions about the behaviour of macrocycles incorporated into separation processes.
  • the data base for macrocycle-cation interaction can be used in choosing a macrocycle for recovering a particular cation.
  • the selective removal and recovery of Pb2+ and Ba2+ from aqueous solutions using 18-crown-6 bonded to silica gel are examples of a suitable choice of macrocycle for a specific need.
  • the data base measurements indicate that Pb2+ and Ba2+ are selectively complexed by 18-crown-6 by at least an order of magnitude over all other cations.
  • the selectivity over cations often present in large excess (i.e. Na+, K+, Mg2+, Ca2+) is much greater.
  • the equilibrium constant values in Table 1 confirm the suitability of the choice of 18-crown-6 as an appropriate macrocycle for the task.
  • the 18-crown-6 bonded silica gel has been tested for its ability to remove Pb2+ from H2O.
  • the desired ion(s) are attached to the silica gel column they must be removed using a small volume of a receiving phase so that a concentrated and purified product is obtained.
  • 99% of the purified Pb2+ and Sr2+ was recovered from the column using 25 ml of a concentrated basic solution of either ethylenediamine tetraacetate (EDTA), citrate, or acetate.
  • EDTA ethylenediamine tetraacetate
  • These reagents form stronger complexes with the ion(s) than the macrocycle does. Hence, they can effectively strip ion(s) from the macrocycle.
  • These ion-receiving phase reagent complexes are easily broken by adding acid to the solution. These species can be recovered as a solid if desired.
  • the Pb2+ can be recovered as a solid by using H2SO4 as the acid and, hence, precipitating PbSO4.
  • Table 3 indicates a range of specific macrocycle ligands and a range of cations with which they interact, to which ligands the present invention may be applied.

Claims (8)

  1. Composition de matière comprenant une silice liée de façon covalente à un composé macrocyclique et avant les formules I, II, III, IV ou V ci-dessous:
    Figure imgb0024
     dans laquelle A à F représentent chacun séparément un atome d'oxygène ou un atome de soufre ou un groupe N-R dans lequel R représente un atome d'hydrogène ou un groupe alkyle ou un groupe aryle, n est 0, 1, 2, 3 ou 4, Z représente une silice ou un gel de silice et X représente un groupe alkyle ou un groupe aryle ou un groupe alkoxyle ou un atome d'halogène ou un groupe O-silice ou un groupe O-gel de silice, et Y représente un atome d'oxygène ou un groupe CH₂; ou
    Figure imgb0025
     dans laquelle A à F représentent chacun séparément un atome d'oxygène ou un atome de soufre ou un groupe N-R dans lequel R représente un atome d'hydrogène ou un groupe alkyle ou un groupe aryle, l, m, et n sont 0, 1 ou 2, Z représente une silice ou un gel de silice, X représente un groupe alkyle, ou un groupe aryle ou un groupe alkoxyle ou un atome d'halogène ou un groupe O-silice ou un groupe O-gel de silice, et Y représente un atome d'oxygene ou un groupe CH₂: ou
    Figure imgb0026
     dans laquelle n est 0, 1 ou 2, Z représente une silice ou un gel de silice, X représente un groupe alkyle ou un groupe aryle ou un groupe alkoxy ou un atome d'halogène ou un groupe O-silice ou un groupe O-gel de silice, et Y un atome d'oxygène ou un groupe CH₂; ou
    Figure imgb0027
     dans laquelle n est 0, 1 ou 2, Z représente une silice ou un gel de silice, R représente un groupe alkyle ou un groupe aryle, X représente un groupe alkyle ou un groupe aryle ou un groupe alkoxyle ou un atome d'halogène ou un groupe O-silice ou un groupe O-gel de silice, et Y représente un atome d'oxygène ou un groupe CH₂; ou
    Figure imgb0028
     dans laquelle l est 0, 1 ou 2, Z représente une silice ou un gel de silice, R représente un atome d'hydrogène ou un groupe alkyle ou un groupe aryle, X représente un groupe alkyle ou un groupe aryle ou un groupe alkoxyle ou un atome d'halogène ou un groupe O-silice ou un groupe O-gel de silice, et Y représente un atome d'oxygène ou un groupe CH₂.
  2. Composition de matière selon la revendication 1, dans laquelle la silice représente du sable.
  3. Composition de matière selon la revendication 1 ou 2, dans laquelle dans la formule I, A à F représentent chacun un atome d'oxygène, n est 0, 1 ou 2 et X représente un groupe méthyle ou un atome de chlore ou un groupe O-silice ou un groupe O-gel de silice, et dans la formule II, A à F représentent chacun un atome d'oxygène, l, m et n sont chacun 1, et X représente un groupe méthyle ou un atome de chlore ou un groupe O-silice ou un groupe O-gel de silice.
  4. Composition de matière selon la revendication 1 ou 2, dans laquelle dans la formule 1, A, C, D et F représentent chacun un atome d'oxygène et B et E représentent chacun tout groupe N-R dans lequel R représente un atome d'hydrogène ou tout groupe alkyle ou tout groupe benzyle, n est 0, 1 ou 2, et X représente un groupe méthyle ou un atome de chlore ou un groupe O-silice ou un groupe O-gel de silice.
  5. Composition selon la revendication 1 ou 2, dans laquelle dans la formule II, A à F representent chacun un atome d'oxygène, m et n sont chacun 1 et l est 0, 1 ou 2 et X représente un groupe méthyle ou un atome de chlore ou un groupe O-gel de silice et Z représente un groupe O-gel de silice.
  6. Appareil de séparation d'ions contenant comme milieu de séparation une composition de matière selon l'une quelconque des revendications 1 à 5.
  7. Procédé de séparation d'un ion choisi parmi un ensemble d'autres ions dans une solution d'ions multiples, caractérisé par la mise en contact de la solution d'ions multiples avec une composition de matière selon l'une quelconque des revendications 1 à 5 dans des conditions qui entraînent que ladite composition de matière à se complexer avec l'ion choisi et à l'éliminer de ladite solution d'ions multiples, la séparation de ladite solution d'ions multiples à partir de laquelle ledit ion choisi a été éliminé dudit complexe, et la rupture dudit complexe pour libérer et récupérer ledit ion choisi dans un liquide récepteur.
  8. Composition de matière comprenant une silice liée de façon covalente à un composé macrocyclique et ayant la formule ci-dessous:
    Figure imgb0029
     dans laquelle A à D représentent chacun séparément un atome d'oxygène ou un atome de soufre ou un groupe N-R dans lequel R représente un atome d'hydrogène ou un groupe alkyle ou un groupe aryle, Z représente une silice ou un gel de silice et X représente un groupe alkyle ou un groupe aryle ou un groupe alkoxyle ou un atome d'halogène ou un groupe O-silice ou un groupe O-gel de silice, et Y représente un atome d'oxygène ou un groupe CH₂.
EP88308158A 1987-09-04 1988-09-02 Ligands macrocycliques liés à de la silice ou du gel de silice et leur utilisation pour enlever et concentrer sélectivement et quantitativement des ions présents à faible concentration de mélanges contenant d'autres ions Expired - Lifetime EP0306334B1 (fr)

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US5855859A (en) * 1994-06-13 1999-01-05 Memc Electronic Materials, Inc. Gettering agent
US5622568A (en) * 1994-06-13 1997-04-22 Memc Electronic Materials, Inc. Gettering of metals from solution
AUPM632894A0 (en) * 1994-06-21 1994-07-14 Alldredge, Robert Louis Immobilised branched polyalkyleneimines
FR2725382B1 (fr) * 1994-10-05 1997-01-03 Commissariat Energie Atomique Polyazacycloalcanes, complexes tri-, tetra- ou pentaazamacrocycliques, procede de fabrication de ces polyazacycloalcanes substitues ou non et greffes sur un support et utilisations des polyazacycloalcanes
JP3890401B2 (ja) 2000-10-13 2007-03-07 独立行政法人物質・材料研究機構 金属イオンの分離法
FR2928144B1 (fr) * 2008-02-28 2011-09-16 Centre Nat Rech Scient Materiaux pour l'extraction solide/liquide de cations de metaux lourds a base de polyazacycloalcanes n-fonctionnalises supportes
JP5164169B2 (ja) * 2009-03-03 2013-03-13 国立大学法人金沢大学 有害金属汚染物の浄化方法
RU2618295C2 (ru) * 2015-09-09 2017-05-03 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Способ получения сорбента из хлорида аммония

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817783B2 (ja) * 1976-07-08 1983-04-09 日本曹達株式会社 固体表面に担持されたヘテロ巨大環化合物
US4539399A (en) * 1984-07-27 1985-09-03 Advanced Separation Technologies Inc. Bonded phase material for chromatographic separations
FR2570075B1 (fr) * 1984-09-11 1987-10-23 Centre Nat Rech Scient Silice greffee complexante, son procede de preparation et ses applications en chromatographie
DE3644346A1 (de) * 1986-12-19 1987-05-21 Saeulentechnik Dr Ing Herbert Matrixgebundene kronenetherliganden als trennmaterial in der affinitaetschromatographie von nukleinsaeuren

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AU7609091A (en) 1991-08-01
AU606240B2 (en) 1991-01-31
IL86766A0 (en) 1988-11-30
JPH01139142A (ja) 1989-05-31
JP2736256B2 (ja) 1998-04-02
AU2164288A (en) 1989-03-09
DE3872628D1 (de) 1992-08-13
EP0306334A3 (en) 1989-04-26
AU641758B2 (en) 1993-09-30
AU2704188A (en) 1989-05-11
IL86766A (en) 1992-02-16
EP0306334A2 (fr) 1989-03-08
DE3872628T2 (de) 1993-03-11

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